JP2008032749A - X-ray fluorescence spectroscopy system and x-ray fluorescence spectroscopy method - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide systems and methods of X-ray fluorescence spectroscopy systems. <P>SOLUTION: A X-ray fluorescence spectroscopy system 100 includes a source of X-ray radiation 110 and an excitation optical component 120 disposed between the X-ray radiation source 110 and a sample 130 for collecting X-ray radiation from the source and focusing the X-ray radiation to a focal point on the sample to cause at least one analyte in the sample to fluoresce. The system further includes an X-ray fluorescence detector 150 and a collection optical component 140, comprising a doubly curved diffracting optical component disposed between the sample and the X-ray fluorescence detector for collecting X-ray fluorescence from the focal point on the sample and focusing the fluorescent X rays directed toward the X-ray fluorescence detector. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to an X-ray fluorescence (XRF) spectroscopy system and a fluorescence X-ray spectroscopy method, and more particularly, a focused X-ray optical component for forming a focused excitation beam on a sample, and a sample The present invention relates to a fluorescent X-ray spectroscopic system and a fluorescent X-ray spectroscopic method including a focusing monochromator for collecting secondary X-rays from the X-ray.

  X-ray fluorescence (XRF) spectroscopy is widely recognized as a very accurate method for determining the atomic composition of materials, and irradiates a sample with X-rays to produce secondary X-rays emitted from the sample. Done by observing.

  In general, an XRF system consists of an excitation radiation source (X-ray tube or radioisotope), means for detecting secondary X-rays from a sample and determining its energy or wavelength, and a display device for spectral output. . The intensity of secondary X-rays at a certain energy or wavelength is correlated with the concentration of elements in the sample. Computer software is often used to analyze the data and determine the concentration.

  The process begins by illuminating the sample using an x-ray source. As the X-ray photon strikes the sample, the X-ray photon knocks electrons out of the inner shell of the atoms that make up the sample, thereby creating a vacancy that makes the atom unstable. As the electrons move from the outer shell to the inner shell, the atom becomes stable and in this process a characteristic X-ray photon is emitted whose energy is the difference between the two binding energies of the corresponding shell. There are two conventional methods for determining the X-ray spectrum emitted from a sample.

  The first method is energy dispersive spectrometry (EDS), and the second method is wavelength dispersive spectrometry (WDS). In an energy dispersive spectroscopy (EDS) system, an energy dispersive detector, such as a solid state detector or a proportional counter, is used to determine the energy spectrum of photons emitted from the sample. Wavelength dispersive spectroscopy (WDS) systems also use crystals or multilayer structures to select unique X-ray wavelengths from X-ray photons emitted from a sample.

  U.S. Patent No. 6,057,031 discloses an energy dispersive (EDS) system that uses only polychromatic optical components in both the detection and collection paths. There is no disclosure of diffractive optics in the excitation or collection path.

  Patent Document 12 is also strictly an EDS system. Even when monochromatic excitation is used, the detection path is not limited to a particular wavelength having a detection optical component, and there is no detection optical component disclosed by this patent document 12. Thus, the detection system encounters a wider band of wavelengths and processes this wider band using conventional EDS technology.

  Patent Document 13 discloses a WDS system, but as described above, Patent Document 13 discloses a conventional technique for illuminating a very large sample area, a pinhole for defining an angle of incidence on an optical component 22. / Slit 6 is disclosed and therefore the collection solid angle is severely limited. There is no disclosure or suggestion of focusing optics that provide a small sample spot size and the attendant advantages of the present invention. The small sample point size of the present invention is “placed” at position 6, but the collection solid angle of the detection optics is not limited.

  Non-Patent Document 1 is the same as Patent Document 12 described above. Even when monochromatic excitation is used in which the detection path is a detection optical component and is not limited to a specific wavelength, this non-patent document 1 does not disclose a detection optical component.

  Patent Document 14 is similar to the monochromatic excitation of Patent Document 12 having a standard EDS detection method.

US Pat. No. 5,175,755 US Pat. No. 5,192,869 US Pat. No. 5,497,008 US Pat. No. 5,570,408 US Pat. No. 5,604,353 US Pat. No. 5,745,547 US Pat. No. 6,285,506 US Pat. No. 6,317,483 US Patent Application No. 09 / 667,966 (filed on September 22, 2000) US Patent Application No. 60 / 336,584 (filed December 4, 2001) US Provisional Patent Application No. 5,982,847 International Publication No. 02/25258 Pamphlet EP0339913 US Provisional Patent Application No. 5,406,609 Chen, et al, "Microprobe X-Ray Fluorescence with the Use of Point-Focusing Diffractors, Appl. Phys Lett. 71 (13) 1884-1886, Sept. 1997

  X-ray fluorescence using EDS is the most widely used elemental concentration analysis. This method has several advantages. First, the EDS detector can detect almost all elements of the periodic table simultaneously. Secondly, the system is compact because no additional optical components are required on the collection side compared to wavelength dispersive X-ray fluorescence systems. Third, since the EDS detector has a large collection solid angle and high efficiency, it is possible to use a low power x-ray tube.

  However, XRF / EDS systems have drawbacks, including relatively poor sensitivity and insufficient energy resolution. Also, since the EDS detector sees all x-rays from the sample, the detector is easily saturated by fluorescence signals from the abundant elements and strong scattering of the primary beam.

  X-ray fluorescence using WDS also has several advantages, including higher energy resolution and higher signal-to-background ratio compared to XRF / EDS systems. XRF / WDS is therefore a powerful tool for trace element analysis and applications that require high energy resolution.

  However, conventional XRF / WDS systems have drawbacks, including the need for high power X-ray tubes due to the limitations of WDS that result in low efficiency, and a small collection solid angle. Another disadvantage of conventional WDS systems is that the collecting crystal or multilayer structure only selects a unique X-ray wavelength, and a scanning mechanism or polycrystalline system is required to detect multiple elements. It is. This has the advantage that it is possible to avoid saturation of the detector, but leads to complex alignment. Therefore, XRF / WDS systems typically have the problem of being large, complex and more expensive than XRF / EDS systems.

  Most XRF instruments are generally for analyzing a wide range of elements, but there are many important applications for industrial process control that require the detection of single or limited elements.

  The present invention has been made in view of such a situation, and an object of the present invention is to provide a compact fluorescent X-ray spectroscopic system and fluorescent X-ray that provide ultra-high sensitivity or high-speed analysis for a limited number of elements. It is to provide a spectroscopic method.

  With the present invention comprising an X-ray fluorescence (XRF) spectroscopy system, the disadvantages of conventional methods are overcome and additional advantages are provided. The XRF system includes at least one x-ray radiation source and at least one excitation optic disposed between the at least one x-ray radiation source and the sample. At least one excitation optic collects x-ray radiation from at least one source and stimulates the x-ray radiation to a focal point above the sample to stimulate and fluoresce at least one analyte of the sample. Focus. The XRF system further includes at least one X-ray detector and at least one collection optic. At least one collection optic is between the sample and the at least one X-ray detector for collecting the fluorescent X-rays from the focal point above the sample and directing the fluorescent X-rays to the at least one X-ray detector. At least one doubly curved diffracting optic.

  There are many other embodiments for the XRF spectroscopy system described above. For example, the at least one x-ray radiation source can comprise at least one electron bombardment x-ray source. The at least one excitation optic can comprise at least one focusing polychromatic optic, such as one or more polycapillary optic, and / or at least one focused monochromatic An optical component (focusing monochromatic optic) can be provided. The focusing monochromatic optical component can comprise at least one doubly curved crystal and / or at least one doubly curved multi-layer optic. The focus can have a focus size of less than 500 microns and the sample can be solid or fluid. Further, the sample can be a petroleum-based product, such as gasoline, diesel, crude oil, or lubricating oil. At least one analyte stimulated within the sample can comprise sulfur and / or iron. In addition, X-ray radiation focused on the sample can be incident on the sample at an angle less than the total external reflection angle, as is desirable for total reflection X-Ray Fluorescence (TXRF). X-ray radiation focused on the sample can be incident on the sample at an angle greater than the total external reflection angle, as is desirable for normal fluorescent X-rays.

  In yet another embodiment, including at least one collection optic that directs x-rays of at least one analyte to the detector to determine the concentration of the at least one analyte or the thickness of the sample in the sample. Is possible. Further, the at least one double-sided curved diffractive optical component of the at least one collection optic can include at least one double-sided curved crystal. The at least one double-sided curved crystal can have a Johann geometry, a Johanson geometry, a partial Johannson geometry approximation, or a logarithmic crystal optic (logarithmic) spiral crystal). Further, the at least one double-sided curved diffractive optic can include at least one double-sided curved multilayer optic, which in some embodiments is a doubly curved graded optic or double-sided curved logarithm. It can be a spiral optical component (doubly curved logarithmic spiral optic). Further, the at least one collection optic can be fixed relative to the sample and the at least one x-ray detector. The at least one x-ray detector can be one or more gas proportional counters, one or more scintillation counters, and / or one or more solid state detectors. The one or more solid state detectors may include at least one PIN diode solid state detector.

  In another embodiment, an X-ray fluorescence (XRF) method is disclosed. The XRF method includes providing at least one X-ray source, collecting X-ray radiation from at least one source to stimulate and fluoresce at least one analyte of the sample, Providing at least one excitation optic disposed between at least one x-ray radiation source and the sample to be analyzed for focusing the x-ray radiation to a focal point above the sample, at least one x-ray Providing a detector, comprising at least one double-sided curved diffractive optic for collecting fluorescent X-rays from a focal point above the sample and focusing the fluorescent X-rays toward at least one X-ray detector Arranging at least one collection optic comprising the sample and the at least one X-ray detector is included.

  Other embodiments of the invention are described in detail herein and are intended to be within the scope of the claims. The gist of the present invention is specifically shown in the claims. Other objects, features and advantages of the present invention will become apparent from the following description based on the accompanying drawings.

  In general, one embodiment of the compact XRF / WDS system of the present invention includes an X-ray source, excitation X-ray optics that focus the X-ray from the source onto the sample, at least one acquisition monochromator, And a line counter. The excitation x-ray optic can be a focused polycapillary optic that provides multicolor excitation, or a point-focused double curved crystal optic that provides monochromatic excitation. A collection monochromator (which can be a double-sided curved crystal optic, a double-sided curved multilayer optic, or other double-sided curved diffractive optic) selects the desired characteristic wavelength of the element. The intensity of the reflected x-ray is measured by a detector and correlates with the concentration of this element in the specimen.

  The XRF / WDS system of the present invention also means that the excitation optics can efficiently obtain a large cone angle of X-rays from a point X-ray source. This excitation optic is a focusing optic that produces a very strong excitation beam even when using a compact, low-power (eg <1 KW, more advantageously <100 W) x-ray source can do. By using a low power X-ray tube, this XRF / WDS system is much more compact and simpler than a conventional XRF / WDS system using a large kw X-ray tube.

  Another embodiment of the present invention is that a monochromatic excitation beam can be generated when a double-sided curved crystal optic is used as the excitation optic. In a typical embodiment of an XRF / WDS system, a sample is excited using a polychromatic beam. Monochromatic excitation provides a much higher signal-to-background ratio than polychromatic excitation because scattered bremsstrahlung from the x-ray source is eliminated on the sample. This significantly improves the detection limit of the XRF / WDS system. Monochromatic excitation also makes the XRF quantitative analysis very simple.

  Another embodiment of the present invention is that the excitation beam is focused on the sample due to the focusing ability of the excitation optics. The focal spot size of the beam on the sample can range from 50μ to 500μ, which is about two orders of magnitude smaller than the beam size of conventional systems (usually 10 mm to 30 mm). In addition to providing efficient acquisition, this smaller beam size allows for spatial resolution in the analysis.

  Due to the smaller excitation area of the sample, double-sided curved diffractive optics can be used efficiently as collection optics (in other embodiments of the invention). Bi-curved monochromatic optics can provide a large collection solid angle from a point. (In conventional XRF / WDS systems with large excitation beam sizes, flat or single-sided curved monochromators are selected and the collection solid angle is limited.) The double-sided curved monochromator allows a given geometry and intensity of the excitation beam. The signal level of the detection element is considerably improved.

  Another embodiment of the invention is that the collection optics can be fixed with respect to the sample and detector without moving the parts involved. This can have both advantages and disadvantages. The advantage is to speed up the analysis and improve the reliability of the system, while the disadvantage is that multiple collection optics may be required, for example, for multi-element analysis.

  That is, according to the present invention, an XRF / WDS system having an X-ray focusing optic that provides multi-color or monochromatic excitation to a sample is disclosed. Secondary X-rays obtained from fluorescent X-rays are collected by a monochromator. The monochromator comprises a double-sided curved diffractive device for transfer to a detector such as a proportional counter, room temperature PIN detector, or NaI detector. One embodiment of an XRF / WDS system that uses monochromatic optics to provide monochromatic excitation and collect x-rays from a sample is described below.

  FIG. 1 is a configuration diagram for explaining an embodiment of the XRF / WDS system of the present invention. The XRF / WDS system 100 includes, for example, a low-power X-ray source 110, a monochromatic focusing optical component 120, a sample 130, a collection monochromator 140, and a detector 150.

  A low power X-ray source 110 (eg, <1 KW, more ideally <100 W) hits an X-ray source, such as an X-ray tube, a radioactive material sealing source, or a metal object, and X It is a high energy electron source that produces line radiation. The low-power X-ray source 110 is, for example, a 50 W X-ray tube, and the target material includes chromium, copper, tungsten, or molybdenum, and the size of the electron beam on the target material ranges from about 50 μm to 300 μm. It is in.

  Sample 130 is a material that is to be weighed. An example of the sample 130 may be a process stream, such as diesel fuel, where sulfur concentration measurement is desirable, or a lubricating oil, where wear metal (iron) concentration measurement is desirable. If sample 130 is a fluid stream, a window material (not shown) may be included to allow X-ray excitation radiation to be transmitted to fluorescent X-rays from sample 130.

  The monochromatic focusing optic 120 disposed between the X-ray source 110 and the sample 130 of the XRF system 100 is several in contrast to polychromatic optics that transmit radiation having an energy bandwidth of thousands of electron volts. Only radiation that is in a small energy region, such as in an energy region between 10 and several hundred electron volts, is useful for reflecting or transmitting to the sample 130. The focusing optic 120 also focuses the x-rays to a small focal point on the sample 130. The focal spot size can range from 50 μm to 500 μm. The focusing optical component 120 is, for example, a Johann double-sided curved crystal.

FIG. 2 is a diagram showing a double-sided curved crystal optic that provides point-to-point focusing for use in the XRF / WDS system of the present invention, showing an example of the geometry of a Johann double-sided curved crystal. In this geometry, the diffractive surface of the crystal 160 is shown parallel to the crystal surface. The crystal plane is annular, has a Johann geometry in the plane of the focusing circle 170, and is axisymmetric along the line SI. Point S is the position of the X-ray source 110 (FIG. 1), and point I is the focal point. The crystal plane has a radius of curvature of 2R in the plane of the focusing circle and a radius of curvature of 2Rsin ² θ _{B in} the intermediate plane perpendicular to the segment SI. R is the radius of the focusing circle, and θ _B is the Bragg angle. X-rays diverge from point S, strike the crystal plane at an incident angle within the rocking curve width of the crystal, and are efficiently reflected at point I. This type of double-sided curved crystal provides not only point focusing of the beam 180 but also monochromation because it can only reflect X-ray photons having the appropriate wavelength.

  As shown in FIG. 1, x-ray optic 140 is another monochromatic optical element of XRF system 100 and is disposed between sample 130 and detector 150. This optical component collects the characteristic wavelength of the X-ray and directs the X-ray to the X-ray detector. In a conventional XRF / WDS system, it is possible to select a flat or one-side curved crystal optical component as the optical component. In the present invention, the collection monochromator is a double-sided curved diffractive device (eg, a crystal optic or multilayer optic) that provides a much larger collection solid angle from the point than a flat / single-sided curved optic. be able to.

  A particular example of collection monochromatic optic 140 is a double-sided curved logarithmic spiral crystal optic.

  FIG. 3A is a diagram showing an example of the geometry of a double-sided curved logarithmic spiral crystal or multilayer optical component used in the XRF / WDS system according to the present invention, and FIG. 3B is a cross-sectional view taken along line BB in FIG. 3A. .

  In this geometry, the diffractive surface of the crystal optical component is parallel to the crystal plane. The crystal plane in the dispersion plane has a logarithmic spiral shape and is rotationally symmetric with respect to the axis ID. Point I is the origin of the logarithmic helix and the focal point of the excitation beam on the sample 130 (FIG. 1), and point D is the position of the detector 150 (FIG. 1). The fluorescent X-rays emitted from point I above the sample have a constant angle of incidence with respect to this logarithmic helical surface due to the nature of the helical curve. This constant angle is selected to be the characteristic X-ray Bragg angle of the target element in the sample 130 with respect to the diffraction plane of the crystal. X-rays reflected from a bilaterally curved logarithmic spiral geometry form a fire line in the dispersion plane, not a point. The X-rays are focused on the axis ID along the ID direction as shown in FIG. 3B.

  As another example, multilayer optics can be used in the XRF / WDS system of FIG. 1 instead of monochromatic optics 120 and collection monochromatic optics 140. The detector 150 can be a simple counting detector, ie a gas proportional counter, a scintillation counter, or a room temperature PIN diode solid state detector.

  Advantageously, the XRF / WDS system 100 is well suited for sensitive trace element analysis. Point-to-point focusing doubly curved crystal provides a large collection solid angle and a very strong focused monochromatic beam on the sample, even when using a low power x-ray tube Form. Due to the monochromatic excitation, the signal background ratio is significantly improved and the detection sensitivity is improved. The point-focusing of the excitation beam onto the sample makes it possible to efficiently use the double-sided curved collection optics to improve the collection solid angle of fluorescent X-rays. This further improves the sensitivity of the XRF / WDS system.

  As one specific example of the XRF / WDS system 100 shown in FIG. 1, the XRF / WDS system can include an X-ray source 110 with a 50 W X-ray tube, where the raw material is chromium , Copper, tungsten, or molybdenum, and the size of the dots on the raw material is about 100 μm to 300 μm. The optical component 120 can be a double-sided curved point-focusing crystal made from silicon, germanium, or other crystalline material and positioned 100 mm to 200 mm from the X-ray source 110 along the optical axis. The optical axis is formed as the line travel center from the X-ray source that strikes the double-sided curved crystal 120, which is the center of the double-sided curved crystal 120.

  Sample 130 may be an oil having trace elements that may include, for example, sulfur, vanadium, and nickel. The sample 130 can be positioned from 100 mm to 200 mm from the monochromatic optical component 120 as measured along the optical axis. The second monochromatic optical component 140 can be a double-sided curved helical crystal made from silicon, germanium, or other crystalline material and positioned along the optical axis from sample 130 to 100 mm from 200 mm. is there. The detector 150 can be a gas proportional counter, a scintillation counter, a room temperature PIN detector, or a NaI detector and can be positioned 100 mm to 200 mm from the sample as measured along the optical axis. is there.

  By adding one or more acquisition monochromators and detectors to the XRF / WDS system 100, more than one element can be detected. Each acquisition monochromator is paired with a detector for each single element detection.

  FIG. 4 is a block diagram for explaining another embodiment of the XRF / WDS system of the present invention, and shows another embodiment of the XRF system 200. The XRF / WDS system 200 includes a source 210, a multicolor focusing optical component 220, a sample 230, a double-sided curved monochromatic optical component 240, and a detector 250.

  The monochromatic optical component 220 is an optical element that transmits a wide range of photon energy and concentrates a small spot on the sample 230 while focusing the photons. An example of a multicolor optical component that is well suited to function as the optical component 220 is a polycapillary optical component 300, such as that available from X-Ray Optical Systems, Albany, NY.

  FIG. 5 illustrates a polycapillary optic that provides point-to-point focusing for use in the XRF / WDS system of the present invention. The polycapillary optical component 300 is described in the above-mentioned patent document, and is a bundle of thin hollow tubes that transmit photons through total reflection.

  Due to the multi-color excitation, the signal to background ratio is insufficient compared to the signal to background ratio of the XRF / WDS system 100 (FIG. 1). However, the XRF / WDS system 200 (FIG. 4) can provide several advantages. For example, in the XRF / WDS system 200, smaller focusing points can be obtained due to the better focusing capability of the polycapillary optics. This may give better spatial resolution for local analysis. For example, a 50 W x-ray tube and polycapillary optics can be used to obtain a 20 μm to 50 μm focus. Another advantage is that polychromatic excitation can provide X-ray photons with a wide range of energies that can cover almost every element of the periodic table.

  In one particular embodiment, the XRF / WDS system 200 can include an X-ray source 210, which can be a 50 W X-ray tube, where the source material is chromium, copper , Tungsten, or molybdenum, and the size of the point on the target material is about 100 μm to 300 μm. The multicolor optical component 220 can be a polycapillary optical component located 30 mm to 50 mm from the X-ray source 210.

  Sample 230 may be an oil having elements that may include, for example, sulfur, vanadium, and nickel. The sample 230 can be placed 100 mm to 200 mm from the polycapillary optical component 220. The double-sided curved monochromator 240 can be a double-sided curved logarithmic spiral crystal manufactured from silicon, germanium, or other crystalline material and positioned along the optical axis and positioned from 100 mm to 200 mm from the sample 230. is there. The detector 250 can be a gas proportional counter, a scintillation counter, a room temperature PIN detector, or a NaI detector positioned along the optical axis and located 100 to 200 mm from the monochromatic optical component 240. Multiple collection monochromators with corresponding detectors can also be used to detect multiple elements.

  While the preferred embodiment has been described above, it will be apparent to those skilled in the art that various modifications, additions, and alternative embodiments can be made without departing from the scope of the claims. .

It is a block diagram for demonstrating one Example of the XRF / WDS system of this invention. FIG. 4 is a diagram showing a double-sided curved crystal optic that provides point-to-point focusing for use in the XRF / WDS system of the present invention, showing an example of the geometry of a Johann double-sided curved crystal. FIG. 4 shows an example of a double-sided curved logarithmic spiral crystal or multilayer optical component geometry for use in an XRF / WDS system according to the present invention. It is a BB line sectional view in Drawing 3A. It is a block diagram for demonstrating the other Example of the XRF / WDS system of this invention. FIG. 5 shows a polycapillary optic that provides point-to-point focusing for use in the XRF / WDS system of the present invention.

Claims (57)

At least one X-ray radiation source (110/210);
At least one X-ray detector (150/250);
Sample (130/230) and X-ray for collecting fluorescent X-rays from a focal point above the sample and directing the fluorescent X-rays of a characteristic energy of a given analyte to the X-ray detector At least one monochromatic collecting optic (140/240) having at least one double-sided curved diffractive optic disposed between the detector;
The X for collecting X-ray radiation from the X-ray radiation source and focusing the X-ray radiation at the focal point above the sample to stimulate the analyte of the sample to generate fluorescence. An X-ray fluorescence spectroscopy system comprising: at least one excitation optic (120/220) disposed between a line radiation source and the sample.   The X-ray fluorescence spectroscopy system of claim 1, wherein the X-ray radiation source (110) comprises at least one electron bombardment X-ray source.   The fluorescent X-ray spectroscopy system according to claim 1, wherein the excitation optic comprises at least one focusing polychromatic optic (220).   4. The fluorescent X-ray spectroscopy system according to claim 3, wherein the focusing polychromatic optical component includes at least one polycapillary optical component.   The fluorescent X-ray spectroscopy system according to claim 1, wherein the excitation optic comprises at least one focusing monochromatic optic (120).   6. The fluorescent X-ray spectroscopic system according to claim 5, wherein the focusing monochromatic optical component includes at least one double-side curved crystal.   6. The fluorescent X-ray spectroscopic system according to claim 5, wherein the focusing monochromatic optical component includes at least one double-side curved multilayer optical component.   The fluorescent X-ray spectroscopy system of claim 1, wherein the focal point has a focal point size of less than 500 microns.   The X-ray fluorescence spectroscopy system according to claim 1, wherein the X-ray radiation focused on the sample is incident on the sample at an angle smaller than a total external reflection angle.   The X-ray fluorescence spectrometer according to claim 1, wherein the X-ray radiation focused on the sample is incident on the sample at an angle greater than a total external reflection angle.   The fluorescent X-ray spectroscopy system according to claim 1, wherein the sample includes a solid.   The fluorescent X-ray spectroscopy system according to claim 1, wherein the sample includes a fluid.   The fluorescent X-ray spectroscopy system according to claim 12, wherein the fluid includes a product mainly composed of petroleum.   The fluorescent X-ray spectroscopy system according to claim 13, wherein the petroleum-based product includes gasoline or diesel.   The fluorescent X-ray spectroscopic system according to claim 13, wherein the product containing petroleum as a main component includes crude oil.   The fluorescent X-ray spectroscopic system according to claim 11, wherein the product mainly composed of petroleum contains lubricating oil.   The X-ray fluorescence spectroscopy system according to claim 1, wherein the at least one analyte includes sulfur.   The X-ray fluorescence spectrometer according to claim 1, wherein the at least one analyte includes iron.   The collection optic (140/240) directs the x-rays of the analyte to the x-ray detector to determine the analyte concentration of the sample or the thickness of the sample. Item 2. The fluorescent X-ray spectroscopy system according to Item 1.   The fluorescent X-ray spectroscopy system according to claim 1, wherein the double-sided curved diffractive optical component includes at least one double-sided curved crystal.   21. The X-ray fluorescence spectrometer according to claim 20, wherein the double-sided curved crystal comprises at least one double-sided curved crystal having a Johann geometric shape.   21. The XRF spectroscopy system of claim 20, wherein the double-sided curved crystal comprises at least one double-sided curved crystal having a Johansson geometry or a partial Johansson geometry approximation.   21. The X-ray fluorescence spectrometer according to claim 20, wherein the double-sided curved crystal comprises at least one double-sided curved logarithmic spiral crystal optical component.   2. The fluorescent X-ray spectroscopy system according to claim 1, wherein the double-sided curved diffractive optical component comprises at least one double-sided curved multilayer optical component.   25. The XRF spectroscopy system of claim 24, wherein the double curved multilayer optical component comprises at least one double curved log helical optical component.   The fluorescent X-ray spectroscopic system according to claim 1, wherein the double-sided curved diffractive optical component includes at least one double-sided curved distributed diffractive optical component.   X-ray fluorescence spectroscopy system according to claim 1, characterized in that the collection optics (140/240) are fixed relative to the sample and fixed relative to the X-ray detector.   The X-ray fluorescence spectrometer according to claim 1, wherein the X-ray detector includes at least one gas proportional counter.   The fluorescent X-ray spectroscopy system according to claim 1, wherein the X-ray detector includes at least one scintillation counter.   The fluorescent X-ray spectroscopy system according to claim 1, wherein the X-ray detector includes at least one solid-state detector.   31. The XRF spectroscopy system of claim 30, wherein the solid state detector comprises at least one PIN diode solid state detector.   The X-ray fluorescence spectrometer according to claim 1, wherein the X-ray detector includes a non-energy sensitive detector.   2. The X-ray fluorescence spectroscopy according to claim 1, wherein the double-sided curved diffractive optical component is arranged such that an input focal point at a focal point of the sample corresponds to an output focal point of at least one excitation optical component. system. Providing at least one X-ray radiation source (110/210);
Providing at least one X-ray detector (150/250);
At least one double-sided diffraction for collecting fluorescent X-rays from the focal point above the sample and directing the fluorescent X-rays of a characteristic energy of a predetermined analyte to the at least one X-ray detector Placing at least one monochromatic collecting optic (140/240) comprising an optic between the sample (130/230) and the X-ray detector;
The x-ray for collecting x-ray radiation from the x-ray source and focusing the x-ray radiation at the focal point on the sample to stimulate and fluoresce the analyte of the sample A method of X-ray fluorescence spectroscopy comprising providing at least one excitation optic (120/220) disposed between a radiation source and a sample to be analyzed.   35. The X-ray fluorescence spectroscopy method of claim 34, wherein the X-ray radiation source (110) comprises at least one electron bombardment X-ray source.   35. The XRF spectroscopy method of claim 34, wherein the excitation optic comprises at least one focusing polychromatic optic (220).   37. The fluorescent X-ray spectroscopy method according to claim 36, wherein the focusing polychromatic optical component includes at least one polycapillary optical component.   35. The XRF spectroscopy method of claim 34, wherein the excitation optic comprises at least one focused monochromatic optic (120).   The fluorescent X-ray spectroscopy method according to claim 38, wherein the focusing monochromatic optical component includes at least one double-sided curved crystal.   The fluorescent X-ray spectroscopy method according to claim 38, wherein the focusing monochromatic optical component includes at least one double-side curved multilayer optical component.   35. The XRF spectroscopy method of claim 34, wherein the focal spot has a focal spot size less than 500 microns.   The fluorescent X-ray spectroscopy method according to claim 34, wherein the sample includes a solid.   The X-ray fluorescence spectroscopy method according to claim 34, wherein the sample includes a fluid.   44. The fluorescent X-ray spectroscopy method according to claim 43, wherein the fluid contains a product mainly composed of petroleum.   45. The fluorescent X-ray spectroscopy method according to claim 44, wherein the petroleum-based product includes gasoline or diesel.   46. The XRF spectroscopy method of claim 45, wherein the at least one analyte includes sulfur.   The X-ray fluorescence spectroscopy method according to claim 34, wherein the double-sided curved diffractive optical component includes at least one double-sided curved crystal.   48. The fluorescent X-ray spectroscopic method according to claim 47, wherein the double-sided curved crystal includes at least one double-sided curved crystal having a Johann geometric shape.   48. The XRF spectroscopy method of claim 47, wherein the double-sided curved crystal comprises at least one double-sided curved crystal having a Johansson geometry or a partial Johansson geometry approximation.   48. The X-ray fluorescence spectroscopy method according to claim 47, wherein the double-sided curved crystal comprises at least one double-sided curved logarithmic spiral crystal optical component.   35. The fluorescent X-ray spectroscopy method according to claim 34, wherein the double-sided curved diffractive optical component comprises at least one double-sided curved multilayer optical component.   52. The X-ray fluorescence spectroscopy method according to claim 51, wherein the double-side curved multilayer optical component includes at least one double-side curved logarithmic spiral optical component.   The X-ray fluorescence spectroscopy method according to claim 34, wherein the double-sided curved diffractive optical component comprises at least one double-sided curved distributed diffractive optical component.   35. The X-ray fluorescence spectroscopy method according to claim 34, wherein the X-ray detector includes at least one gas proportional counter.   35. The X-ray fluorescence spectroscopy method according to claim 34, wherein the X-ray detector includes at least one scintillation counter.   The X-ray fluorescence spectroscopy method according to claim 34, wherein the X-ray detector comprises a non-energy sensitive detector.   35. X-ray fluorescence spectroscopy according to claim 34, wherein the double-sided curved diffractive optical component is arranged such that an input focal point at the focal point of the sample corresponds to an output focal point of at least one excitation optical component. Method.

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